The present invention relates to inorganic matrix compositions incorporating a silicate network, which can be processed at conditions comparable to those used for typical high-performance organic polymer processing (temperatures ˜15° C. to ˜200° C. and pressures <200 psi), although a wide range of temperatures and pressures can be employed. The physical and thermal properties of the inorganic matrix binder as well as composites may be enhanced by elevated processing temperatures (up to 400° C. and greater) and pressures (up to 20,000 psi and greater) to produce exceptional composite and neat resin components. The composite materials formed at the lower processing conditions exhibit excellent thermal, dimensional, physical and flameproof properties.
Inorganic matrices are useful as flame retardant binders, bulk materials, adhesives, cellular materials, such as foamed materials, or composite materials. As bulk materials, they are used to form shaped objects which when cured provide a structural material. As a composite material, the matrix composition is used to impregnate a fabric, which may be combined with other similarly impregnated fabrics, to form the composite lay-up, which is then shaped and cured to form a shaped object, similar to a bulk material, but with the benefit of the reinforcement provided by the fabric.
The basic concept of composite materials has been known for centuries. Composite materials offer a unique blend of value added features, such as weight savings, electrical insulation, thermal insulation, corrosion resistance, and manufacturing cost savings. These features in some instances can overshadow the material cost in specialized applications ranging, for example, from sporting equipment to the F-22 aircraft fuselage. However, current state-of-the-art composite materials can also exhibit properties that present serious barriers to entry in some high-performance markets. These include poor flame, smoke and toxicity (FST) performance, physical degradation at high temperatures as well as higher material and processing costs. When exposed to fire or high temperatures (>500° C.), conventional composite materials can combust and generate toxic smoke and/or gases. The exceptions, such as ceramic matrix composites and metal matrix composites, are too expensive (often more than $500/lb) to gain a significant market presence. Clearly, a market need exists for affordable high temperature-resistant, insulating structures.
The most familiar composite systems today are based on organic polymer matrices such as epoxy/glass fiber, epoxy/carbon fiber, polyurethane/glass fiber, PVC/glass fiber, polyimide/quartz fiber, polyester/glass fiber and nylon/glass fiber. Although organic polymer composites exhibit excellent physical and mechanical properties, they are limited with regard to flammability, smoke and gas generation and elevated service temperatures. The flammability of organic polymer-based composites can be reduced by the addition of inorganic components and/or additives. The substitution of hydrogen atoms with halogen atoms (e.g. chlorine) in hydrocarbons and hydrocarbon polymers can significantly reduce flammability and smoke/gas generation but will degrade at high temperatures (>250° C.) and eventually incinerate at higher temperatures (>450° C.). Organic thermoplastic polymers also deform at relatively low temperatures (˜100° C.-300° C.) and organic polymers designed for higher service temperatures are generally prohibitive in material and processing costs.
Other composite materials include metal matrix composites (MMC), ceramic matrix composites (CMC), carbon-carbon composites as well as other inorganic matrix composites. A composite matrix may be 100% inorganic, or it may contain some organic content. Inorganic matrix networks include ceramics, silicates, glasses, aluminum silicates, alkali aluminum silicates, potassium silicates, sodium silicates, silicon carbides, silicon nitrides, alumina, cementitious materials, metals, metal alloys or other matrix materials known to those knowledgeable in the arts. Other materials can be considered include inorganic particles encapsulated with inorganic binders, organic resins filled with inorganic fillers, inorganic-organic hybrids such as silicone, and other inorganic matrix materials known to those knowledgeable in the arts.
A disadvantage of organic polymers is their deficiencies at high temperatures. The use of metals and ceramics raises additional questions with regard to thermal and electrical conductivity, weight limitations, toughness, dielectric properties, ductility, and processing options. Further, ceramics do not lend themselves to the low temperature processing procedures as contrasted with organic polymer processing.
A need exists for noncombustible, temperature-resistant inorganic polymer compounds which process at temperatures and pressures typical for organics (<200° C. and <200 psi) which combines the desirable features of ceramics (non-flammability, resistance to temperatures >450° C.) and organic polymers (low-temperature processing, complex shapes).
Alkali silicates are employed as affordable inorganic matrix binder materials. See for example, U.S. Pat. Nos. 4,472,199; 4,509,985; 4,888,311; 5,288,321; 5,352,427; 5,539,140; or 5,798,307 to Davidovits; U.S. Pat. No. 4,936,939 to Woolum; or U.S. Pat. No. 4,284,664 to Rauch. However, alkali silicates typically possess a very high pH. Thus, these alkali solutions are so caustic that they damage glass fibers, severely degrading strength. Furthermore, cured composite samples prepared in accordance to these disclosures still exhibit a high pH in a solid form. Rauch has disclosed the addition of nonreactive borosilicate glass to an alkali silicate solution, but the glass mentioned is Pyrex, a material that is typically considered inert.
U.S. Pat. No. 3,933,689 to Ray et al relates to the addition of a low softening point glass of Tg 300° C. and optionally to a blowing agent for a reinforced thermosetting composite to impart fire retardant properties.
U.S. Pat. No. 3,935,018 to Ray relates to inorganic oxide glasses having compositions within the range (in moles percent) B2 O3 1.2-3.5, P2 O5 50-72, PbO 0-30, transition metal oxides 0-5, the remainder being oxides selected from alkali metal oxides, alkaline earths and zinc oxide.
U.S. Pat. No. 3,964,919 to Ray relates to phosphate glasses containing minor amounts of the oxides of chromium, molybdenum and tungsten (Group VIb) are within the range (moles percent) P2 O5 50-75 Group VIb oxides 0.1-10, comprising singly or in combination CrO3 up to 2.6, MoO3 up to 7, WO3 up to 7. At least one oxide selected from alkali metal oxides and alkaline earths 15-49.9. Addition of oxidizing agents (e.g. sodium nitrate) to the melt may be used to keep the Group VIb metals in the hexavalent state.
U.S. Pat. No. 3,989,532 to Ray relates to an optical article, for example, a lens, window or mirror, at least part of the surface of which, and preferably the whole of which, is an inorganic oxide glass having a P2 O5 content of at least 52 mole %, and preferably 55 to 68.5 mole %, an alkaline earth content of 2.7 to 20 mole %, and a transformation temperature of not greater than 300° C., the glass optionally containing B2 O3 and at least one alkali metal oxide.